Process and apparatus for eliminating higher-boiling-point impurities prior to rectification of a gas mixture



m m I M w G 1951 R. w. HOUVENER PROCESS AND APPARATUS FOR ELIMINATING HIGHER-BOILING POINT IMPURITIES PRIOR TO RECTIFICATION OF A Filed May 20, 1949 3 Sheets-Sheet l R E N Q w W n m m w n L A a fim U R w R Q \r 3 \w .v 2356 zuoombz Oct. 30, 1951 R. w. HOUVENER 2,572,933

PROCESS AND APPARATUS FOR ELIMINATING HIGHER-BOILING POINT IMPURITIES PRIOR TO RECTIFICATION OF A GAS MIXTURE Filed May 20, 1949 3 Sheets-Sheet 2 OXYGEN INVENTOR RUSSELL W. HOUVENER ATTORNEY N IT Oct. 30, 1951 Filed May 20, 1949 IOR TO RECTIFICATION OF A GAS MIXTURE r 3 Sheets-Sheet 3 I g. %z

{a J. 4 J, N i a V g Q I m N l N gil 1* m 45 L m i IINVENTOR 8 $3 A 1:. RUSSELL W. HOUVENER EJHP 1 1 z ATTORNEY Patented Oct. 30, 1951 PROCESS AND APPARATUS FOR ELIMINAT- IN G HIGHER-BOILING-POINT IIHPURITIES PRIOR TO RECTIFICATION OF A GAS m- TURE Russell W. Houvener, Kenmore, N. Y., assignor, by mesne assignments, to Union Carbide and Carbon Corporation, a corporation of New York Application May 20, 1949, Serial No. 94,308

moisture and carbon dioxide, but small amounts of other higher-boiling point impurities that are normally gaseous, such as hydrocarbons. Moisture is eliminated usually by freezing it out during early stages of heat exchange, and in the case of 14 Claims. (Cl. 62-122) regenerator heat exchange, a large part of the carbon dioxide may also be frozen out and removed by vaporization into outfiowing products. Residual amounts of carbon dioxide and impurities in a finely divided frozen state which remain in air cooled to about liquefaction temperatures can be removed from the air by washing or scrubbing the air with liquid air and filtering the scrubber liquid. In practice it is found that small amounts of impurities nevertheless still reach the rectifying columns and are concentrated, particularly in the chamber where the oxygen product is boiled. In a gaseous oxygen producing plant especially, the chamber where the oxygen is evaporated collects residual impurities. One method of preventing excessive impurity accumulation is to periodically or continuously withdraw and discard some of the impurity-containing concentrate. Even with such withdrawal of oxygen product deposition of impurities on heat exchange surfaces is not prevented, and it is found that such deposition is very undesirable, especially in rectifying apparatus designed to operate at high efliciency.

It appears that certain small residues of carbon dioxide and hydrocarbon impurities remain in solution in liquid air and thus are not filterable. When dissolved impurities are concentrated at the low temperature of evaporating oxygen they are thrown out of solution. When scrubber liquid is filtered and passed to rectification columns the minute dissolved residues are washed down in the column eventually to the oxygen product which is partly evaporated in a chamber around the main condenser to provide vapors for rectification. In a gaseous oxygen producing plant, the liquid oxygen is completely evaporated to produce the product. Such concentration and evaporation causes deposition of solids to occur on heat- 2 ing surfaces, which not only i detrimental to efllciency but may also be hazardous.

Principal objects of the present invention are to provide a process and apparatus for eliminating impurities from a gas mixture such as air prior to its low-temperature separation, which avoids the above-mentioned diillculties; which provides for the practically complete removal of impurities from all of the gas mixture that is to be rectified: which not only substantially completely cleans a scrubber liquid of impurities but also avoids the passage of any scrubber liquid to the rectification; and which provides these advantages without any material additional operating cost or any effect on the efliciency of separation. v

These and other objects and advantages of this invention will become apparent from the following description and the accompanying drawings, in which the figures are diagrammatic views showing exemplary embodiments of apparatus for carrying out the processes of the invention. particularly for the separation of air to produce a gaseous oxygen product, and wherein:

Fig. 1 is a diagrammatic view of an assemblage of apparatus in which the invention is applied in a plant for producing gaseous oxygen of commer cial purity with lower power cost; a

Fig. 2 is a similar view of a modification of the apparatus according to the invention; and

Fig. 3 is a diagrammatic view illustrating the principles of the invention as applied in a plant employing air compressed to an initial pressure higher than the critical pressure of air and producing liquid oxygen.

In the practice of the present invention, gas

mixtures such as air containing impurities are compressed and cooled as usual through any suitable countercurrent heat exchangers or cold accumulators in such a manner that moisture and a large part of the carbon dioxide are removed. The cooled air is then scrubbed or washed with liquid air under a pressure below the critical pressure of air. Such scrubbing is preferably carried out countercurrently in a thorough manner, so that the air is washed last by the cleanest available scrubber liquid. The impurity-free air is then further treated to prepare for the rectification, for example, some of the cleaned air may be fed directly as gaseous feed to a higher-pressure chamber of the rectifying apparatus, and in cycles where it is necessary to provide extra refrigeration, some of the cleaned air may be expanded, after indirectly reheating it, by a turbine expander and then delivered to the lower pressure the concentration of them excessively in scrubber.

liquid is prevented by free circulation. of the scrubber. liquid from the scrubber through a flitering device or an adsorption medium, or preferably successively through a filter and an adsorber and then back to the scrubber.

If a filter alone is used, the dissolved impurities are recirculated with the liquid until the concentration becomes such that they are thrown out of solution and thereupon they are retained on the filter medium, which may be cleaned by providing duplicate filters so that one can be thawed and cleaned while the other is on-stream. It is found that certain impurities such as acctylene of limited solubility in liquid air may accumulate in the liquid to such a concentration before precipitating that their partial vapor pressure equals the partial pressure of such impurities in the air before his scrubbed. In such case the impurity would pass through the scrubber and enter the rectifying column with the scrubbed air. By using an adsorption medium, preferably preceded by a filter, dissolved impurities can also be removed and the scrubber liquid returned to the scrubber will be very clean, so that the scrubbing can be more effective and the chance of carrying impurities out with the scrubbed air greatly reduced. The invention is lower pressure stages; and

. D. A refrigeration-producing means.

The air is compressed by suitable means such as a rotary compressor In to about a condensation pressure preferably between 95 p. s. i. and 35 p. s. i. and conducted by a conduit H to the warm ends of regenerator pairs l2 and I3. From the cold end of the regenerator pairs, the air is conducted by conduit to the lower end of awash tower or scrubber column IS. .The regenerators may be similar to those disclosed in the United States patent of M. Frankl No. 1,970,299.

A large portion of the clean scrubbed air from lit duit 2b to the upper end of the column II, the conduit being controlled by a transfer valve 25'. Preferably there may be interposed in the conduit a. heat exchange passage or coil 25 in a heat exchanger ,21 that is.- interposed in the uent nitrogen conduit 28 from the top of the col o' 26.. Also interposed in the etlluent nitrogen conduit is a heat exchanger 29 employed for liq w-1r clean air, and after leaving the heat excer 29 the conduit 28 conducts the eflluent nitrogen to the cold end of the regenerator pair [12 for passage therethrough and discharge at conduit 3d.

liquid air, a portion of clean conducted by a conduit 3! to a heat excw e coil 32 within the heat exchanger 29 and liquid air condensed in the coil 32 is conducted by a conduit .33 to a conduit 38 below conduit 85 and which has a branch 3| connecting with conduit l6 so that a large portion of the liquid flow to the conduit 16 and be carried wlth cl r air to the high-pressure chamber flii. Another branch of the conduit 34 which is controlled by a valve 35 enters the top of the sober 65 so that the valve 35 may be opened whenever it is desired to add clean fresh scrubber liquid to the scrubber column l5. Valve 85 may be regulated to provide a continuous flow in amounts necessary to provide make-up for scrubbed air. To this end conduit 36 draws clean scrubbed air from the upper end of the scrubber is to one end of a. heat exchanger pair 31, 31' which heats the scrubbed air portion suniciently so that refrigeration is produced with high efliciency and substantially no condensation 'of air. The wed air is conducted by conduit 38 to an expon turbine 39 coupled in a customary in to means not shown for absorbing the power produced. The work-expanded air is conducted by a conduit d0, preferably to an intermediate portion of the column 2!. A normally closed icy-pass connection M between conduits 6d and 2d may be provided for use when initially cooling down the plant.

the top of the scrubber column I5 is conducted by conduit l6 into the higher pressure chamber [1 of the two-stage rectifying apparatus C, which may be substantially of the customary type. The chamber I! may have gas and liquid contact trays l8 therein and is closed at the top by a condenser I 9 which condenses a portion of the lower-boiling nitrogen component by'heat exchange with liquid oxygen product in a chamber 20 surrounding the condenser l9 and forming the lower end of the low-pressure rectifying column 2|. Liquid rich in oxygen collecting at the base of the high-pressure chamber I1 is transferred to an intermediate point of the column 2| by a conduit 23 controlled by transfer valve 23'. Some of the liquid produced by the condenser is is collected in the shelf 24 and transferred by. 091i- The owgen product may be drawn as a gas from the chamber 2B, but as shown in Fig. 1, it is preferably produced by conducting liquid omgen from the chamber 20 through conduit 43 to an evaporator chamber 46 connected also by a pressure-equalizing connection 45 with the gas space of th chamber 20. I'he chamber M may be heated by suitable means, for example, by a condenser 63 therein which is supplied with clean scrubbed air through a branch conduit d7 of the conduit l6. Aircondensed in the condenser 46 is drained by conduit 68 to the high-pressure chamber ill. The oxygen vapors from the evaporator it are conducted by a conduit 89 to a heat exchanger hii and from the heat exchanger 50 through a conduit 5! to the cold end of the regenerator pair l3, from the warm end of which the oxygen product is withdrawn from a conduit 52. Disposed within the heat exchanger 50 is a heat exchange coil 53 connected to receive clean scrubbed air from the conduit 3! and to deliver liquid air to the conduit 39.

The heat exchangers 31 may be heated by a suitable warmer fluid stream, for example, a portion of air may be tappedoff at an intermediate point of the rcgeneratorsand conducted bye conduit 56 to the warm end of a heat exchange passage 56 in the heat exchanger 31 and the cooled tapped-off portion of air is conducted by conduit 51 to the lower end of the scrubber I5.

None of the used scrubber liquid is passed to the rectification apparatus 0, but the scrubber liquid is cleaned by withdrawing same from the bottom of the scrubber I through a conduit 66 which has interposed therein a rotary pump 6| designed for moving such cold liquids as liquid air. For example, the pump may be similar to that described in United States Patent No. 2,296,640. The liquid is preferably forced by the pump 6| through a filter 62 and then by a conduit 63 to one end of a chamber 66 filled with a suitable adsorbent substance, and from the other end of the chamber 64 the treated scrubber-liquid is returned to the scrubber at a high point thereof by conduit 65. The filters and the adsorber chambers are preferably provided in duplicate in order that one of the respective pair may be taken out of service for cleaning while the other is in service. The adsorbent material in the chamber 66 is a material having the property of adsorbing dissolved impurities such as dissolved carbon dioxide and hydrocarbons from the liquid air passed therethrough. A suitable material, for example, is silica gel, and suitable means such as connections 61 and 66 to the chambers 64 may be provided for use in reactivating the silica gel of one of the chambers after a period of use. The silica gel may be retained between transverse screens in the chambers 64 and 64'.

The use of filters 62 is not essential, since the adsorbent material in the chamber 66 will retain the small particles of solid impurities as well as adsorb the dissolved impurities. However, the filters 62 generally are preferable to reduce the load on the adsorbent, since they will remove the bulk of the larger solidified particles of impurities. It will be seen that all the air which is to be rectified is thoroughly cleaned and is washed last by very clean scrubber liquid. Therefore the heat exchange surfaces, particularly those of the condensers I9 and 46, are protected against deposition of solid materials which would seriousl reduce the eiiiciency of the apparatus and constitut a hazard. The impurities are eiilciently and safely removed by concentrating them in a relatively small amount of scrubber liquid which is recirculated and from which the impurities are continuously removed so that the air may be washed by very clean scrubber liquid. Also, because only a relatively small amount of scrubber liquid need be recirculated, the filters and adsorbing device may be relatively small and eflicient. The amount of power required for effecting the recirculation by pump 6| is so small as to be relatively immaterial. A is customary, all cold apparatus is thoroughly protected from atmospheric heat by efiicient insulation.

In the figures, similar features are designated by similar reference characters. In the modification of Fig. 2, the main heat exchange system chamber 'II and forces the liquid through the filters 62 and one or the other of a pair of adsorbers I64. From the opposite end of the adsorbers I 64 the conduit I65 conducts the clean scrubber liquid to an intermediate point of the scrubber II5. For providing exceptionally pure scrubber liquid for the top of the scrubber H6 a branch 13 of conduit I65 conducts some of the initially cleaned scrubber liquid to one end of an adsorber chamber H, from the other end of which a conduit I5 connects with the upper end of the chamber H5. The conduit 15 is controlled by a valve 15' and a control valve I6 is preferably provided in the conduit I65 on the downstream side of the branch 13.

The operation of the clean-up system of Fig. 2 is simflar to that of Fig. 1, with the addition that the valves 15' and I6 may be regulated so that only a small portion of the recirculated scrubber liquid passes through the adsorber I4 and the main work of impurity removal occurs in the adsorber I64 or in both the filter 62 and adsorber I66. By providing very clean liquid at the top of the scrubber II5 the impurity vapor pressure at the upper end of scrubber H5 will be negligible so that practically no vapor phase impurities will leave with the scrubbed air; also there will be no likelihood of transfer of impurities through the cleaned air by entrainment of fine particles of scrubber liquid therein. Gaseous oxygen product is withdrawn from chamber 20 by conduit I 5| to the oxygen regenerator pair I3.

The system of impurity removal according to the present invention is also adaptable to other types of air rectification apparatus, for example, one producing liquid oxygen, as described in connection with Fig- 3. In Fig. 3, the compressor III) may be of the staged type providing compressed air at pressures above the critical pressure. Such compressed air may be cooled by a customary type heat exchange system A, for example, by conducting it through conduit 2| I to heat exchange passages in heat exchangers 2|! arranged particularly for removal of moisture by freezing. A portion of the intermediately cooled air is conducted by a conduit 2| 3 to another heat exchange set 66 which cools it to a very low temperature, such that when expanded a substantial fraction becomes liquid. Such cold air, which is entirely gaseous and contains particles of frozen impurities, is passed by a conduit 2| 4 into the lower part of a scrubber chamber 2I5. The conduit 2 has interposed therein an expansion valve 8| through which the air is throttle expanded immediately prior to passage into the scrubber 2I5 which collects the resulting liquid fraction.

Another portion of air for providing extra refrigeration is conducted by a branch conduit 82 to an expansion engine 83 and from thence into the scrubber 2 I 5 by conduit, 84. Since it is necessary that a considerable portion of the air feed to the rectifying column C be in the liquid state .7 (corresponding to the product taken out in the liquid state), the scrubber system is arranged to operate at a higher pressure than the pressure of the first stage of rectification and a portion of scrubbed air is liquefied before it is fed to the column by heat exchange with scrubber liquid boiling at the pressure of the first stage of rectification. The rectifying column apparatus indicated generally at C may be of the customary type for producing liquid oxygen and has. a liquid oxygen withdrawal connection 85 from the lower part of the chamber 20. Clean scrubbed air from the top of the scrubber 215 may be conducted by a conduit 23l to a heat exchange coil 232 in a vaporizer chamber 86. Clean liquid air produced in the coil 232 is conducted with a remainder of vaporous air through conduit 2 l 6 into the first stage chamber ll of the rectifying apparatus, there being an expansion valve 81 interposed in conduit 2l6. The scrubber liquid that overflows into a cup 88 passes through a valved connection 89 into the vaporizing chamber dd wherein it is vaporized by liquefying a corresponding amount of the cleaned air passing through coil 232. The vapors which pass to the top of chamber 86 are conducted by conduit at to the first stage chamber l1.

.- A substantially constant quantity of residual scrubber liquid is recirculated in the system. This flows from chamber 86 through the conduit 28!) to the suction of the pump 26l and from.

thence through the filters 262 and the adsorbers 266 and back to chamber 86. Preferably the purified scrubber liquid is divided and part is passed by conduit ill to the upper end of scrubber chamber 2? and the other part is passed by conduit 92 to the upper end of vaporizer cham-.

ber 86, the conduits being controlled by valves 9! and 92' respectively. The upper portions of the chambers M5 and 86 are also preferably provided with gas washing trays 93 and 94 to insure that all the air passed to the rectifying column will have been washed last by liquid air containing' the least impurities. In this system the pressure in chamber 2I5 would preferably be about 60 p. s. i. higher than the pressure in chamber 35 which is about that of the first stage of rectification. Hence there is a pressure reduction of that amount at valves 81 and 89 and also at valve 92'.. The pump 26! provides the necessary boost in pressure and the valve 9| may be operated substantially open while the valve $2 is adjusted to regulate the amount of liquid bypassed to chamber 86. If desired the conduit @il may connect to an intermediate part of the upper column 21 instead of to lower column i? so that the pressure in chamber 86 need be only that of the upper column and the scrubber 2 l 5 may then operate under a pressure only slightly above that of the lower column IT. The eiliuent nih'ogen, as is customary, is passed to the cold end of main heat exchanger 80 by the conduit 28 and from the warm end thereof through a conduit $5 to the cold end of heat exchanger 212 and to the atmosphere from the warm end thereof through conduit 95.

It will be seen that the invention provides for the practically complete removal'of the minute amounts of impurities in air, particularly the most undesirable impurities including acetylene, before the air enters the rectifying apparatus so that no accumulation of impurities will occur in liquid oxygen or on the oxygen vaporizing surfaces. This is accomplished in part by not adinitting any scrubber liquid to the rectifying column and especially by scrubbing the air that is fed to the column with a scrubber liquid that is substantially free of dissolved impurities. The

invention is especially useful for gaseous oxygen producing plants but may be used in liquid oxygen producing plants without seriouslyincreasing the operating cost.

While several embodiments of exemplary apparatus have been describedin order to disclose the principles of the present invention, it is contemplated that modifications may be made in the process and apparatus without departing from the pirit and scope of the invention.

What is claimed is:

1. A process for eliminating higher-boiling impurities from a. gas mixture such as air before it is subjected to low-temperature rectification, which process comprises providing a stream of the mixture under pressure, freed of moisture, and cooled to alow temperature; washing such stream at a condensation pressure below '150 p. s. i. with a scrubber liquid to remove the impurities from said gas stream and retain them in the scrubber liquid; forming the scrubber liquid by liquefaction of part of the scrubbed gas mixture; and eliminating impurities from said scrubber liquid by passing used scrubber liquid from the washing in intimate contact with an adsorbent material which selectively retains the impurities.

2. A process for eliminating higher-boiling impurities from a gas mixture such as air. before it is subjected to low-temperature rectification, which process comprises providing a stream of the mixture under pressure, freed of moisture, and cooled to a low temperature; washing such stream at a condensation pressure with a scrubber liquid comprising a liquid fraction of the gas mixture to remove the impurities from said gas stream and retain them in the scrubber liquid; continuously eliminating impurities from said scrubber liquid by recirculating used scrubber liquid from the washing in intimate contact with an adsorbent material which selectively retains the impurities; and returning the cleaned scrubber liquid to said washing operation.

3. A process for separating a gas mixture according to claim 2 in which said washing is carried out in successive stages, said cleaned sombber liquid being returned to the initial stage of washing, and in which fresh scrubber liquid is supplied to a later stage of the washing.

a. A process for separating a gas mixture according to claim 2, in which said washing is carried out in successive stages, and said contact of scrubber liquid with adsorbent is effected in successive stages, a large portion of the liquid passing an earlier stage of contact being returned to an earlier stage of the washing and the liquid passing the later stage of contact being returned to a later stage of the washing.

5;. A process for eliminating higher-boiling impurities froma gas mixture such as air before it is subjected to low-temperature rectification, which process comprises providing a stream of the mixture under pressure, freed of moisture, and cooled to a low temperature; washing such stream at a condensation pressure below p. s. i. with a liquefied fraction of said gas mixture to remove the impurities from said gas stream and retain them in the scrubberliquid; continuously removing the impurities from said scrubber liquid in successive stages, the solidified impurities being substantially removed by filtration in a first stage and the remaining impurities being removed in a. subsequent stage by adsorption in an adsorbing medium, the used liquid being recirculated through said stages and returned to the washing.

6. A process for separating a gas mixture according to claim 5, in which said liquid fraction is produced substantially by fractional liquefaction of gas mixture after it has been washed and in which such liquid fraction is added to a later zone of the washing.

7. A process for separating a gas mixture containing higher-boiling impurities which comprises providing a stream of the mixture at a condensation pressure, freed of moisture, and cooled to a low temperature; countercurrently washing such stream with a liquefied fraction of said gas mixture to remove the impurities from said gas stream and retain them in the scrubber liquid; continuously eliminating impurities from said scrubber liquid by recirculating used scrubber liquid from the washing in intimate contact with an adsorbent material which selectively retains the impurities; returning the cleaned scrubber liquid to said washing operation; liquefying a portion of the clean washed gas mixture, using a portion of the liquefied mixture to replenish scrubber liquid evaporated during the washing; rectifying the balance of the washed gas mixture with the remainder of the liquefied portion thereof to separate lower and higherboiling products, and using some of the refrigeration of at least the lower-boiling separation product to effect said partial liquefaction of the washed gas mixture.

8. A process for eliminating higher-boiling impurities from a gas mixture such as air before it is subjected to low-temperature rectification, which process comprises providing a stream of the mixture under pressure, freed of moisture, and cooled to a low temperature; washing such stream at a condensation pressure below 150 p. s. i. with a liquefied fraction of said gas mixture to remove the impurities from said gas stream and retain them in the scrubber liquid; continuously eliminating impurities from said scrubber liquid by recirculating used scrubber liquid from the washing in intimate contact with an adsorbent material which selectively retains the impurities; effecting liquefaction of a substantial portion of the clean washed gas mixture; and rectifying the balance of the washed gas mixture with such liquefied portion thereof to separate lower and higher boiling products.

9. A process for separating a gas mixture according to claim 8 in which said liquefaction of washed mixture is effected by heat exchange with scrubber liquid to vaporize an equivalent amount of the scrubber liquid and in which the vapor of the scrubber liquid is added to the rectifying operation. a

10. Apparatus for eliminating higher-boiling impurities fror rya gas mixture such as air after it is cooled to a low temperature in heat exchange 10 liquid from a lower part of the washing means, through said adsorbent chamber and back to the washing means.

11. Apparatus for eliminating higher-boiling impurities from a gas mixture such as air after it is cooled to a low temperature in heat exchange devices and before it is delivered to a rectifying column, which apparatus comprises means disposed between the heat exchange device and the rectifying column for countercurrently washing a stream of the cooled and substantially moisture-free gas mixture at, a pressure below 150 p. s. i. with scrubber liquid comprising a liquid fraction of the gas mixture to remove the impurities from the gas mixture and retain them in the scrubber liquid; a filter device adapted to retain solid particles of impurities; a chamber containing an adsorbent material adapted to remove the impurities from the scrubber liquid; and means for recirculating scrubber liquid from a lower part of the washing means, through said filter device and then through said adsorbent chamber and back to the washing means.

12. Apparatus for eliminating higher-boiling impurities from a gas mixture such as air after it is cooled to a low temperature in heat exchange devicesand before it is delivered to a rectifying column, which apparatus comprises devices and before it is delivered to a rectifying means disposed between the heat exchange device and the rectifying column for countercurrently washing a stream of the cooled and substantially moisture-free gas mixture at a pressure below p. s. i. with scrubber liquid comprising a-liquid fraction of the gas mixture to remove the impurities from the gas mixture and retain them in the scrubber liquid; a chamber containing an adsorbent material adapted to remove the impurities from the scrubber liquid; a second chamber containing adsorbent material; and means including conduit connections for recirculating used scrubber liquid from a lower part of said washing means through said first adsorbent chamber, then delivering a. part of the scrubber liquid to an intermediate part of said washing means, and for passing the balance of the scrubber liquid through the second adsorbent chamber and then to the upper portion of said washing means.

13. Apparatus for eliminating higher-boiling impurities from a gas mixture such as air after it is cooled to a low temperature in heat exchange devices and before it is delivered to a rectifying column, which apparatus comprises means disposed between the heat exchange device and the rectifying column for washing a stream of the cooled and substantially moisturefree gas mixture at a condensation pressure with scrubber liquid comprising a liquid fraction of the gas mixture to remove the impurities from the gas mixture and retain them in the scrubber liquid; a chamber containing an adsorbent material adapted to remove the impurities from the scrubber liquid; means for recirculating scrubber liquid from a lower part of the washing means, through said adsorbent chamber and back to the washing means; and means for passing to the rectifying column only clean washed gas mixture and liquefied washed gas mixture.

14. Apparatus for eliminating higher-boiling impurities from a gas mixture such as air after it is cooled to a low temperature in heat exchange devices and before it is delivered to a rectifying column, which apparatus comprises means disposed between the heat exchange device and the 7 rectifying column for washing a stream of the masses .cooled and substantially moisture-free mix= tin-e at a condensation pressure with scrubber liquid comprising a liquid traction oithe gas mixture to remove the impurities fiom the gas mixture and retain them in the sber liquid; a chamber containing an adsorbent material adapted to remove the impurities from the semi:- -ber liquid; means for recirculating seruleber liquid from a lower part 01' the washing means, through said adsorbent chamber and back to the washing means; means for liquefying a portion of the clean washed gas mixture by heat exchange with recirculating scrubber iiquid; and means for passing to the rectifying eel the remaining washed gas mixture, the liquefied mm as m Number 12 tion of washed gas mixture and vapors produced by said heat exchange.

RUSSELL w. HOUVENER.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Name Date 1,724,513 Pollitzer Aug. 13, 1929 1,864,585 De Bauire June 28. 1932 1,891,125 Gessel Dec. 13, 1932 2,128,692

De Bauire Aug. 30, 1938 

